Acetylated derivatives of dialdehydes and of their hemiacetals as gelatin hardeners



United States Patent ACETYLATED DERIVATIVES 0F DIALDEHYDES AND OF TIERHEMIACETALS AS GELATIN HARDENERS Roy Arthur Jefireys, Harrow, and DonaldM. Bnrness, Wealdstone, Middlesex, England, assignors to Eastman KodakCompany, Rochester, N.Y., a corporation of New Jersey No Drawing. FiledAug. 21, 1963, Ser. No. 303,664

5 Claims. (Cl. 106-125) This invention relates to gelatin compositionscontaining therein as a hardener a diacyloxy compound of a certain type.

Various compounds have been suggested as gelatin hardeners. Some ofthese compounds have exhibited properties of one kind or another whichlimited their use in certain situations. For instance, formaldehyde hasshown desensi-tizing characteristics in contact with certain highlysensitized photographic emulsions. eners have been so efiective thatthickening of gelatin coating compositions occurs very shortly after thehardener addition, hence, the urgency of almost immediate coating. Somehardeners have had toxic effects and have been avoided where possible inmanufacturing operations. Other hardeners have shown tendencies to fogand stain photographic elements with passage of time.

One object of our invention is to provide compositions which will givehardened gelatin layers but which do not exhibit thickening uponincorporating the hardener in the coating composition. Another object ofour invention is to provide hardeners for gelatin-silver halidephotographic emulsion which do not adversely aifect their sensitivityand do not fog or stain the emulsions. A further object of our inventionis to provide gelatin coating compositions which provide layers whichretain a high degree of flexibility upon storage or aging. Other objectsof our invention will appear herein.

We have found that certain diacyloxy compounds added to gelatincompositions exert a hardening effect upon gelatin layers formedtherefrom, particularly upon aging or the like of those layers. Almostany amount of these hardeners will exert hardening on the gelatin but toobtain a substantial hardening advantage it is desirable that at least0.1% and preferably .55%, based on the weight of the gelatin, beincorporated in the gelatin coating composition.

The hardeners in accordance with our invention are represented by thefollowing type formulas in which acetyl is used as the acyl group. Ifdesired, other acyl groups may be employed but the acetoxy compounds arepreferred having been found to be quite convenient for use as hardeners:

073.000 OOOGH;

CH(CHZ)nCH R0 OR in which R is an alkyl of 14 carbon atoms and n equals0-5.

(IJH OH H-O CH OH3000 O OCOOH Other hard- "ice CH =CHZ O OGOCHQ Thegelatin compositions such as photographic gelatinsilver halidephotographic emulsions containing a hardener in accordance with theinvention may be coated out onto a support such as paper, film base orthe like, to form photographic elements.

The following examples illustrate the preparation of some hardenersuseful in hardening gelatin in accordance with our invention.

Example 1 Mixed 1,1,2,2-diacetoxydiethoxyethane isomers were prepared byrefluxing a mixture of 1,1,2,2-tetraethoxyethane and acetic anhydrideplus a drop of methylsulphate as the catalyst. See the article byFiesselmann and Horndler, Chem. Ber., 87, 911, (1954).

Example 2 Twenty-two ml. of 1,1,3,3-tetraethoxypropane was mixed with20' ml. of acetic anhydride and one drop of methylsulphate was addedthereto. The mixture was refluxed overnight. The product was thendistilled yielding mixed 1,1,3,3-diacetoxydiethoxypropane isomers.

Example 3 Thirty grams of 1,1,2,2-tetramethoxyethane was reacted with 42ml. of acetic anhydride with one drop of methyl sulphate by the methoddescribed in the preceding example. The product obtained afterdistillation of the reaction mixture was fractionally crystallized frompetroleum distillate (B.P., 60-80 to give the isomers of1,1,2,2-diacetoxydi methoxyethane, M.P. 77 and 51, described byFiesselmann and Horndler, Chem. Ber., 87, 908, 911 (1954).

Example 4 2,5-diacetoxy-2,S-dihydrofuran was prepared by the methoddescribed by Clauson-Kaas, U.S. Patent No. 2,514,026.

Example5 2,3-diacetoxy-1,4-dioxane was prepared by the method ofBoeseken, Tellegen and Henriquez, J. Amer. Chem. Soc, 55, 1284, (1933).

The above hardeners were added to portions of a fine grain negativegelatino-silver bromoiodide emulsion in the proportions specified, theproperties obtained being indicated in the following table. The emulsionoriginally contained 67% gelatin and the final emulsion pH Was asdesignated.

Final emulsion pH 8.4

Fog Cont. Rel. M.P. M.P. Speed F.) F.)

Control 0. 31 0. 98 4. 30 92 93 Control+2,3-diaeetoxy-1,4-dioxan(O.3g./1.) 0. 23 0. 95 4. 38 90 93 Control+2,8-diacetoxy-1,4-dioxan(1.0g./1.) 0. 23 0. 96 4. 30 94 100Control-{234iiaeetoxy-L4-clioxan (3.0g./l.) 0. 22 0.92 4.33 105 123Contr01+2,5-diaeetoxy-2,5-dihydrofuran (03.g./1.) 0. 25 0. 98 4.30 92155 Control+2,5-d1acet0xy-2,5-dihydrofuran (1.0g./1.) 0.21 0.02 4.30 92200 Control+Example 1 product (O.3g./l.) 0.34 0.98 4. 93 190Control-i-Exarnple 1 product (1.0g./1.) 0.28 0. 96 4. 2-0 94 197Control-l-Exemple 1 product (3.0g./1.) 0. 24 0. 94 4. 20 94 200Control+diacetoxydimethoxy ethane (m.p.

77") (0.3g. 0. 32 0. 98 4. 18 88 164 Control+diacetoxydimethoxy ethane(m.p.

77) (1. 1. 0. 27 0.94 4. 23 90 200 Control+diacetexydimethoxy ethane(m.p.

77) (3. ./1. 0.23 0. 94 4. 27 101 200 Contro1+diaoetoxydimethoxy ethane(m.p.

51) (0. ./1. 0.27 0.98 4. 28 90 180 Oontrol+diacetoxydimethoxy ethane(m.p.

51) .Og. 0.26 0.98 4.32 96 200 Control+diacetoxydirnethoxy ethane (m.p.

51) (2.0g./1.) 0. 24 0. 99 4. 26 96 200 Control+diacetox ample 2)(0.3g./l.) 0.29 0.98 4.20 96 200 (2.) Tested 7 days after coating. (b)Coatings tested alter incubation at 42% RH. and 120 F. for 2 weeks.

Final emulsion pH 8.5

Fog Rel. M.P. Speed F.)

ControL 0.36 4.12 96 30 Control+2,3-diacetoxy-1,4-dioxan (0.3g./1.) 0.30 4. 21 100 Control+2,3-diacetoxy-1,4dioxa.n (1.0g./1.) 0.31 4. 16 120Control+2,3-diaeetoxy-1,4-dioxan (3.0g./1.)- 0. 34 4. 05 160 (o)Coatings tested after 3 months. 35

Final emulsion pH 8.4

Fog Cont. Rel. M.P. M.P. Speed 0 F.) F.)

Control 0. 22 0.99 4. 20 94 105 Control+2,5-diaeetoxy-2,5-dihydrofuran(0 3g,/1 0. 20 0. 97 4. 22 96 1 Control+2.5-diacet0xy-2,5-dihydrofuran(1,0 /1) 96 200 Control+2,5-diaoetoxy-2,S-dihydroiuran (3 Og,/l. 0.17 o93 4. 21 96 2 0 Control+diacetoxydimethoxy ethane (m.p.

77) (0.3g. O. 22 0.98 4. 25 Oontrol+diacetoxydimethoxy ethane (n1.p.

77) (1.0g./1.) 0.20 1.02 4.24 90 130 Control-i-diaeetoxydimethoxy ethane(m.p.

77 )(3.0g./1.) 0. 22 0.91 4. 22 90 180 Control+diaoetoxydietl1oxypropane (Example 2) (0.3g./1.) 0.22 0.97 4.26 96 200 (2.) Tested 7 daysafter coating.

(1)) Coatings tested after incubation at 42% RH. and F. or 2 weeks.

Final Emulsion pH Six Month Keeping Test pH 6.5 pH 8.5

Fog Rel. M.P. Fog Rel. M.P. Speed F.) Speed F.)

. Contr 0. 25 4. 32 0. 38 4. 26 Control+2,3-diacetoxy-1,4-dioxan (0.3 0.24 4.26 150 0.39 4. 22 Oontrol+2,3-diaoetoxy-l,4-dioxan (1.0g 0. 25 4.28 155 0. 32 4. 16 200 Control+2,3-diaeetoxy-1,4-dioxan (3.0g./l.) 0.214. 28 0.30 4.06 200 Melting points were determined by immersing theelement containing the gelatin coating in water and increasing thetemperature until disintegration of the coating occurred.

We claim: 1. A composition of matter composed of gelatin containing ahardener selected from the group consisting of omooo ooooH3 CH(CHz)nCHBO OR in which R is an alkyl of 1-4 carbon atoms and n=0-5;

OHQC OZCH=OHOH=CHO C O CH;

and

(EH 0 O2CH=CHCH2CH=CHO O OCH;

References Cited by the Examiner UNITED STATES PATENTS 2,585,596 2/1952Stanton 96l11 2,870,013 1/1959 Harrow 96--100 3,241,972 3/1966 Wilson96-111 MORRIS LIEBMAN, Primary Examiner.

D. I. ARNOLD, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 291,624 December 13, 1966 Roy Arthur Jeffreys et a1 a It is hereby certifiedthat error appears in the above numbered patent requiring correction andthat the said Letters Patent should read as corrected below.

Column 1, lines 53 to S7, for the right-hand portion of the formulareading OOOCH read OCOCH same column 1, lines 60 to 63, the formulashould appear as shown below instead of as in the patent:

CH CH c CHSCOO/ \O/:\OCOCH3 column 2, lines 1 to S, the formula shouldappear as shown below instead of as in the patent:

H-2-CH2 columns 3 and 4, in the heading to the third table, first columnfor "804" read 605 ---n CH COO OCOCH Signed and sealed this 24th day ofOctober 1967.

(SEAL) Attest:

EDWARD J., BRENNER EDWARD MGFLETCHERJRO Commissioner of PatentsAttesting Officer

1. A COMPOSITION OF MATTER COMPOSED OF GELATIN CONTAINING A HARDENERSELECTED FROM THE GROUP CONSISTING OF